supplementary materials


bt6938 scheme

Acta Cryst. (2013). E69, m600    [ doi:10.1107/S1600536813027852 ]

Di-[mu]-hydroxido-[kappa]4O:O-di-[mu]-perchlorato-[kappa]4O:O'-bis­[(2,2'-bi­pyridine-[kappa]2N,N')copper(II)]

B. Saravanan, A. Jayamani, N. Sengottuvelan, G. Chakkaravarthi and V. Manivannan

Abstract top

In the title binuclear copper(II) complex, [Cu2(ClO4)2(OH)2(C10H8N2)2], the CuII ion is coordinated in the form of a Jahn-Teller distorted octahedron by two bi­pyridine N atoms, two perchlorate O atoms and two hydroxide O atoms, and displays a distorted octa­hedral geometry. The mol­ecule belongs to the symmetry point group C2h. The CuII ion is located on a twofold rotation axis and the hydroxide and perchlorate ligands are located on a mirror plane. Within the dinuclear mol­ecule, the Cu...Cu separation is 2.8614 (7) Å. The crystal structure exhibits O-H...O, C-H...O and [pi]-[pi] [centroid-centroid distance = 3.5374 (13) Å] inter­actions.

Comment top

Copper complexes have received much attention because of their interesting interactions with biological ligands to generate stable mixed coordinated complexes, which play a key role in life processes such as enzymatic catalysis, storage and conveyance of the matter, transfer of copper ions (Müller et al., 2003; Lo et al., 2000). In the molecular structure of the title compound (Fig. 1), the bond distances Cu1—N1 = 1.9865 (16) Å and Cu1—O1 = 1.9097 (13) Å agree with the reported similar structures (Shaikh et al., 2012; Wang et al., 2010). Each Cu(II) cation is hexa-coordinated with two N atoms of bipyridine, two hydroxyl group O atoms bridging the copper cations and two O atoms of perchlorate anions, showing distorted octahedral environment (Fig. 1). The molecule belongs to the symmetry point group C2h. The two copper anions are separated by a distance of 2.8614 (7) Å, indicating a strong CuII···CuII interaction which is comparable with the CuII···CuII distance in the reported structure (Li et al., 2009).

The crystal structure is stabilized by O—H···O, C—H···O (Fig. 2 & Table 1) and ππ [Cg1···Cg1i distance = 3.5374 (13) Å; (i) -2-x, y, -z; Cg1 is the centroid of the ring (N1/C1/-C5)] interactions.

Related literature top

For the biological activity of copper complexes, see: Müller et al. (2003); Lo et al. (2000). For related strucutures, see: Li et al. (2009); Shaikh et al. (2012); Wang et al. (2010).

Experimental top

To a solution of 2,2'-bipyridine (0.25 g, 1.60 mM) in 10 mL methanol, Cu(ClO4)2. 6H2O (0.59 g, 1.60 mM) in 10 mL of methanol, was slowly added dropwise with constant stirring. The mixture was stirred well at room temperature for about 3 h, the formed blue solution was then concentrated to one third of its volume, washed well (with water, methanol and ether) and dried under vacuum. The complex was then recrystallized in ethanol by the slow evaporation method to obtain X-ray quality single crystals of the complex, which appeared gradually after several days.

Refinement top

The H atom of the hydroxyl O atom was located in a difference Fourier map and refined with the O1—H1 distance restrained to 0.82 (1)Å. All other H atoms were positioned geometrically and refined using riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

One reflection (1 1 0) was omitted from the final cycles of refinement owing to poor agreement.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms. Symmetry codes : (a) -2-x, y, -1-z; (b) -2-x, -y, -1-z; (c) x, -y, z.
[Figure 2] Fig. 2. The packing of the title compound, viewed down a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.
Di-µ-hydroxido-κ4O:O-di-µ-perchlorato-κ4O:O'-bis[(2,2'-bipyridine-κ2N,N')copper(II)] top
Crystal data top
[Cu2(ClO4)2(OH)2(C10H8N2)2]F(000) = 676
Mr = 672.36Dx = 1.878 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 4012 reflections
a = 13.6014 (12) Åθ = 3.2–28.3°
b = 15.2064 (13) ŵ = 2.08 mm1
c = 6.2738 (6) ÅT = 295 K
β = 113.587 (3)°Block, colourless
V = 1189.19 (19) Å30.24 × 0.20 × 0.18 mm
Z = 2
Data collection top
Bruker Kappa APEXII
diffractometer
1516 independent reflections
Radiation source: fine-focus sealed tube1330 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω and φ scansθmax = 28.3°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1717
Tmin = 0.635, Tmax = 0.706k = 2018
4520 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0419P)2 + 0.8702P]
where P = (Fo2 + 2Fc2)/3
1516 reflections(Δ/σ)max < 0.001
95 parametersΔρmax = 0.44 e Å3
1 restraintΔρmin = 0.31 e Å3
Crystal data top
[Cu2(ClO4)2(OH)2(C10H8N2)2]V = 1189.19 (19) Å3
Mr = 672.36Z = 2
Monoclinic, C2/mMo Kα radiation
a = 13.6014 (12) ŵ = 2.08 mm1
b = 15.2064 (13) ÅT = 295 K
c = 6.2738 (6) Å0.24 × 0.20 × 0.18 mm
β = 113.587 (3)°
Data collection top
Bruker Kappa APEXII
diffractometer
1330 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Rint = 0.022
Tmin = 0.635, Tmax = 0.706θmax = 28.3°
4520 measured reflectionsStandard reflections: 0
1516 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077Δρmax = 0.44 e Å3
S = 1.03Δρmin = 0.31 e Å3
1516 reflectionsAbsolute structure: ?
95 parametersAbsolute structure parameter: ?
1 restraintRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.96779 (13)0.27374 (12)0.3726 (3)0.0316 (4)
C20.93192 (16)0.34870 (14)0.2418 (3)0.0415 (4)
H20.94680.40390.31150.050*
C30.87311 (17)0.34058 (17)0.0041 (4)0.0481 (5)
H30.84740.39030.08770.058*
C40.85328 (16)0.25859 (17)0.0941 (4)0.0469 (5)
H40.81510.25200.25360.056*
C50.89063 (16)0.18601 (16)0.0462 (3)0.0429 (5)
H50.87670.13030.02070.052*
N10.94650 (12)0.19315 (11)0.2767 (2)0.0331 (3)
O10.95484 (16)0.00000.2803 (3)0.0416 (5)
O20.75740 (19)0.00000.7997 (4)0.0547 (6)
O30.79963 (14)0.07747 (11)0.5234 (3)0.0566 (4)
O40.63781 (17)0.00000.4095 (4)0.0584 (6)
Cl10.74892 (5)0.00000.56343 (11)0.03846 (17)
Cu11.00000.09408 (2)0.50000.03551 (13)
H10.8987 (16)0.00000.167 (4)0.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0339 (8)0.0310 (9)0.0312 (9)0.0004 (7)0.0143 (7)0.0011 (7)
C20.0480 (11)0.0352 (10)0.0402 (10)0.0028 (8)0.0163 (9)0.0054 (8)
C30.0491 (11)0.0519 (14)0.0398 (11)0.0063 (10)0.0139 (9)0.0167 (10)
C40.0411 (10)0.0649 (15)0.0299 (9)0.0013 (10)0.0093 (8)0.0043 (10)
C50.0442 (10)0.0481 (12)0.0330 (9)0.0068 (9)0.0118 (8)0.0047 (9)
N10.0373 (7)0.0311 (8)0.0297 (7)0.0038 (6)0.0122 (6)0.0013 (6)
O10.0478 (11)0.0305 (10)0.0335 (10)0.0000.0027 (8)0.000
O20.0678 (14)0.0552 (14)0.0335 (11)0.0000.0123 (10)0.000
O30.0610 (10)0.0435 (9)0.0628 (11)0.0040 (7)0.0223 (8)0.0070 (8)
O40.0420 (11)0.0687 (16)0.0470 (13)0.0000.0004 (10)0.000
Cl10.0394 (3)0.0367 (3)0.0315 (3)0.0000.0061 (3)0.000
Cu10.0431 (2)0.02606 (18)0.0349 (2)0.0000.01302 (14)0.000
Geometric parameters (Å, º) top
C1—N11.345 (2)N1—Cu11.9865 (16)
C1—C21.375 (3)O1—Cu11.9097 (13)
C1—C1i1.484 (3)O1—Cu1ii1.9097 (13)
C2—C31.388 (3)O1—H10.807 (10)
C2—H20.9300O2—Cl11.440 (2)
C3—C41.369 (4)O3—Cl11.4372 (17)
C3—H30.9300O4—Cl11.431 (2)
C4—C51.376 (3)Cl1—O3iii1.4372 (17)
C4—H40.9300Cu1—O1ii1.9097 (13)
C5—N11.342 (2)Cu1—N1i1.9865 (16)
C5—H50.9300Cu1—Cu1ii2.8614 (7)
N1—C1—C2121.81 (16)Cu1—O1—H1123.4 (12)
N1—C1—C1i114.25 (10)Cu1ii—O1—H1123.4 (12)
C2—C1—C1i123.94 (11)O4—Cl1—O3109.45 (9)
C1—C2—C3118.8 (2)O4—Cl1—O3iii109.45 (9)
C1—C2—H2120.6O3—Cl1—O3iii110.11 (15)
C3—C2—H2120.6O4—Cl1—O2108.83 (15)
C4—C3—C2119.3 (2)O3—Cl1—O2109.49 (9)
C4—C3—H3120.3O3iii—Cl1—O2109.49 (9)
C2—C3—H3120.3O1—Cu1—O1ii82.97 (9)
C3—C4—C5119.13 (19)O1—Cu1—N1i176.89 (8)
C3—C4—H4120.4O1ii—Cu1—N1i97.91 (6)
C5—C4—H4120.4O1—Cu1—N197.91 (6)
N1—C5—C4122.0 (2)O1ii—Cu1—N1176.89 (7)
N1—C5—H5119.0N1i—Cu1—N181.37 (9)
C4—C5—H5119.0O1—Cu1—Cu1ii41.48 (4)
C5—N1—C1118.93 (17)O1ii—Cu1—Cu1ii41.48 (4)
C5—N1—Cu1126.04 (15)N1i—Cu1—Cu1ii139.32 (4)
C1—N1—Cu1115.01 (11)N1—Cu1—Cu1ii139.32 (4)
Cu1—O1—Cu1ii97.03 (9)
N1—C1—C2—C30.7 (3)C1i—C1—N1—Cu12.8 (2)
C1i—C1—C2—C3179.4 (2)Cu1ii—O1—Cu1—O1ii0.0
C1—C2—C3—C40.6 (3)Cu1ii—O1—Cu1—N1176.99 (7)
C2—C3—C4—C51.1 (3)C5—N1—Cu1—O13.53 (17)
C3—C4—C5—N10.4 (3)C1—N1—Cu1—O1178.01 (13)
C4—C5—N1—C10.9 (3)C5—N1—Cu1—N1i179.53 (19)
C4—C5—N1—Cu1177.48 (15)C1—N1—Cu1—N1i1.07 (9)
C2—C1—N1—C51.4 (3)C5—N1—Cu1—Cu1ii0.47 (19)
C1i—C1—N1—C5178.60 (18)C1—N1—Cu1—Cu1ii178.93 (9)
C2—C1—N1—Cu1177.14 (14)
Symmetry codes: (i) x2, y, z1; (ii) x2, y, z1; (iii) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2iv0.81 (2)2.34 (1)3.134 (3)169 (4)
C5—H5···O2iv0.932.523.381 (3)153
Symmetry code: (iv) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.81 (2)2.338 (13)3.134 (3)169 (4)
C5—H5···O2i0.932.523.381 (3)153.4
Symmetry code: (i) x, y, z+1.
Acknowledgements top

The authors thanks the STIC Cochin University of Technology, Cochin, for the data collection. AJ and NS acknowledge the Department of Science and Technology, New Delhi (DST-SR/FT/CS-049/2009).

references
References top

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